Pesticidal mixtures

ABSTRACT

Pesticidal mixtures comprising, as active components,
     1) an anthranilamid compound of the formula I   

     
       
         
         
             
             
         
       
         
         
           
             wherein the variables are defined according to the description, and 
           
         
         2) at least one fungicidal compound II selected from the following groups:
       strobilurins, carboxamides, heterocylic compounds and other active compounds according to the description,
 
in a synergistically effective amount, methods for controlling pests, and harmful fungi, methods of protecting plants from attack or infestation by insects, acarids or nematodes, methods for treating, controlling, preventing or protecting an animal against infestation or infection by parasites, compositions containing these mixtures, and methods for their preparation.

This application is a Continuation application of U.S. patentapplication Ser. No. 12/441,405, filed Mar. 16, 2009, the entirecontents of which is hereby incorporated herein by reference. U.S.patent application Ser. No. 12/441,405 is a National Stage applicationof International Application No. PCT/EP2007/059758, filed Sep. 17, 2007,which claims the benefit of U.S. Provisional Application No. 60/845,382,filed Sep. 18, 2006, and U.S. Provisional Application No. 60/885,273,filed Jan. 17, 2007, the entire contents of which is hereby incorporatedherein by reference

DESCRIPTION

The present invention relates to pesticidal mixtures comprising, asactive components,

1) an anthranilamide compound of formula I

-   -   in which the substituents are as defined below:    -   B¹ is hydrogen, cyano or chlorine;    -   B² is bromine or CF₃; and    -   R is hydrogen or C₁-C₆-alkyl;        and        2) at least one fungicidal compound II selected from the        following groups:    -   A) strobilurins, selected from: methyl        (2-chloro-5-[1-(3-methylbenzyloxy-imino)ethyl]benzyl)carbamate,        methyl        (2-chloro-5-[1-(6-methylpyridin-2-yl-methoxyimino)ethyl]benzyl)carbamate        and methyl        2-(ortho-((2,5-dimethyl-phenyloxymethylene)phenyl)-3-methoxyacrylate;    -   B) carboxamides, selected from: furametpyr, tiadinil,        N-(4′-bromobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide,        N-(4′-trifluoromethylbiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide,        N-(4′-chloro-3′-fluorobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide,        N-(3′,4′-dichloro-4-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide,        N-(3′,4′-dichloro-5-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide;        3,4-dichloro-N-(2-cyanophenyl)isothiazol-5-carboxamide;        N-(2′,4′-difluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;        N-(2′,4′-dichlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;        N-(2′,4′-difluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;        N-(2′,4′-dichlorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;        N-(2′,5′-difluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;        N-(2′,5′-dichlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;        N-(2′,5′-difluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;        N-(2′,5′-dichlorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;        N-(3′,5′-difluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;        N-(3′,5′-dichlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide,        N-(3′,5′-difluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;        N-(3′,5′-dichlorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;        N-(3′-fluorobiphenyl-2-yl)-1-methyl-3-trifluoro-methyl-1H-pyrazole-4-carboxamide,        N-(3′-chlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;        N-(3′-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide,        N-(3′-chlorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carbox-amide;        N-(2′-fluoro-biphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;        N-(2′-chlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;        N-(2′-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;        N-(2′-chlorbiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;        N-(2′-fluoro-4′-chloro-5′-methyl-biphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;        N-(3′,4′,5′-trifluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;        N-(3′,4′,5′-trifluorobiphenyl-2-yl)-1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide;        N-(2′,4′,5′-trifluorobiphenyl-2-yl)-1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide;        N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-chlorofluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;        N-[2-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;        N-[2-(1,1,2,3,3,3-hexafluoropropoxy)-phenyl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide,        N-[2-(2-chloro-1,1,2-trifluoroethoxy)phenyl]-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;        N-[2-(2-chlor-1,1,2-trifluoroethoxy)phenyl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;        N-[2-(1,1,2,2-tetrafluoro-ethoxy)phenyl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;        N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;        N-(4′-(trifluoromethylthio)biphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;        N-(4′-(trifluoro-methylthio)biphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;        5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxylic acid        [2-(1,2-dimethyl-propyl)-phenyl]-amide, flumetover, carpropamid,        and;        N-(2-{4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-methanesulfonylamino-3-methylbutyramide,        N-(2-{4-[3-(4-chlorophenyl)-prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-ethanesulfonylamino-3-methyl-butyramide;    -   C) heterocylic compounds, selected from: aldimorph,        focthilinone, amisulbrom, diclomezine,        5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,        6-(3,4-di-chlorophenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,        6-(4-tert-butylphenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,        5-methyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,        5-methyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,        6-methyl-5-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,        6-ethyl-5-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,        5-ethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,        5-ethyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,        6-octyl-5-propyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,        5-methoxymethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,        6-octyl-5-trifluoromethyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine        and        5-trifluoromethyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine;        2-butoxy-6-iodo-3-propylchromen-4-one; dazomet,        3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine;    -   and    -   D) other active compounds, selected from metam, methyl        3-(4-chlorophenyl)-3-(2-isopropoxycarbonylamino-3-methylbutyrylamino)propanoate;        enilconazole, streptomycin, binapacryl, dinobuton,        fentin-acetate, fosetyl, phosphorous acid and its salts,        hexachlorobenzene, thiophanate-methyl, and copper acetate;        in a synergistically effective amount.

Moreover, the invention relates to a method for controlling pests, thisincludes animal pests and harmful fungi, using mixtures of a compound Iwith active compounds II and to the use of the compounds I with theactive compounds II for preparing such mixtures, and also tocompositions comprising such mixtures.

In one embodiment the present invention provides methods for the controlof insects, acarids or nematodes comprising contacting the insect,acarid or nematode or their food supply, habitat, breeding grounds ortheir locus with a pesticidally effective amount of mixtures of acompound I with one or more compounds II.

Moreover, in another embodiment the present invention also relates to amethod of protecting plants from attack or infestation by insects,acarids or nematodes comprising contacting the plant, or the soil orwater in which the plant is growing, with a pesticidally effectiveamount of a mixture of a compound I with one or more compounds II.

This invention also provides a method for treating, controlling,preventing or protecting an animal against infestation or infection byparasites which comprises orally, topically or parenterallyadministering or applying to the animals a parasiticidally effectiveamount of a mixture of a compound I with one or more compounds II.

The invention also provides a process for the preparation of acomposition for treating, controlling, preventing or protecting awarm-blooded animal or a fish against infestation or infection byinsects, acarids or nematodes which comprises a pesticidally effectiveamount of a mixture of a compound I with one or more compounds II.

Moreover, the invention relates to a method for controlling harmfulfungi using mixtures of a compound I with active compounds II and to theuse of a compound I with active compounds II for preparing suchmixtures, and also to compositions comprising these mixtures.

The anthranilamide compound of formula I referred to above as component1, their preparation and their action against insect and acarid pestsare known (WO 2004/67528; WO 2004/46129; WO 2004/33468; WO 2003/24222;WO 2003/15518).

Mixtures, active against pests, of compounds of formula I with otherinsecticides are known in a general manner from WO 2004/67528; WO2004/46129; WO 2004/33468; WO 2003/24222; WO 2003/15518. WO 2006/055922discloses anthranilamide derivatives as single compounds, and inmixtures. Binary mixtures of compounds of formula I with otherfungicides are described in WO 2006/108552.

The active compounds II mentioned above as component 2, theirpreparation and their action against harmful fungi are generally known(cf.: http://www.hclrss.demon.co.uk/index.html); they are commerciallyavailable. Particularly, they are known from: furametpyr, tiadinil,3′-chloro-4,4′-dimethyl-1,2,3-thiadiazole-5-carboxanilide [CAS RN223580-51-6]; flumetover,2-(3,4-dimethoxyphenyl)-N-ethyl-α,α,α-trifluoro-N-methyl-p-toluamide[AGROW No. 243, 22 (1995)]; carpropamid,2,2-dichloro-N-[1-(4-chlorophenyl)ethyl]-1-ethyl-3-methylcyclopropanecarboxamide[CAS RN 104030-54-8]; aldimorph, 4-alkyl-2,5 (or2,6)-dimethylmorpholine, comprising 65-75% of 2,6-dimethylmorpholine and25-35% of 2,5-dimethylmorpholine, comprising more than 85% of4-dodecyl-2,5 (or 2,6)-dimethylmorpholine, where “alkyl” may alsoinclude octyl, decyl, tetradecyl or hexadecyl and where the cis/transratio is 1:1; octhilinone; amisulbrom,N,N-dimethyl-3-(3-bromo-6-fluoro-2-methylindole-1-sulfonyl)-[1,2,4]triazole-1-sulfonamide(WO 03/053145); diclomezine,6-(3,5-dichlorophenyl)-p-tolyl)pyridazin-3(2H)-one; metam,methyldithiocarbaminic acid (U.S. Pat. No. 2,791,605); streptomycin,O-2-deoxy-2-methylamino-α-L-glucopyranosyl-(1→2)-O-5-deoxy-3-O-formyl-α-L-lyxofuranosyl-(1→4)N1,N3-diamidino-D-streptamine;polyoxins,5-(2-amino-5-O-carbamoyl-2-deoxy-L-xylonamido)-1-(5-carboxy-1,2,3,4-tetrahydro-2,4-dioxopyrimidin-1-yl)-1,5-dideoxy-β-D-allofuranuronicacid and the salts thereof; binapacryl,(RS)-2-sec-butyl-4,6-dinitrophenyl 3-methylcrotonate; dinobuton,(RS)-2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate;dihydronaphtho[2,3-b][1,4]dithiin-2,3-dicarbonitrile (GB 857 383);fentin acetate, triphenyltin acetate (U.S. Pat. No. 3,499,086); fosetyl,(FR 22 54 276); thiophanate-methyl,1,2-phenylenebis(iminocarbonothioyl)bis(dimethylcarbamate) (DE-OS 19 30540).

The compounds named according to IUPAC, their preparation and theirfungicidal activity are likewise known: methyl(2-chloro-5-[1-(3-methylbenzyloxyimino)ethyl]benzyl)carbamate, methyl(2-chloro-5-[1-(6-methylpyridin-2-ylmethoxyimino)ethyl]benzyl)carbamate(EP-A 12 01 648); methyl2-(ortho-((2,5-dimethylphenyloxymethylene)phenyl)-3-methoxyacrylate(EP-A 226 917);5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine(WO 98/46608), 3,4-dichloro-N-(2-cyanophenyl)isothiazole-5-carboxamide(WO 99/24413),N-(2-{4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-methanesulfonylamino-3-methylbutyramide,N-(2-{4-[3-(4-chlorophenyl)prop-2-ynyloxy]-3-methoxyphenyl}ethyl)-2-ethane-sulfonylamino-3-methylbutyramide(WO 2004/049804),N-(4′-bromobiphenyl-2-yl)-4-di-fluoromethyl-2-methylthiazole-5-carboxamide,N-(4′-trifluoromethylbiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide,N-(4′-chloro-3′-fluorobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide,N-(3′,4′-dichloro-4-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide(WO 2003/066609);N-(3′,4′-di-chloro-5-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide(WO 03/053145); 2-butoxy-6-iodo-3-propylchromen-4-one (WO 2003/14103);3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine (EP-A 10 35122); amisulbrom,N,N-dimethyl-3-(3-bromo-6-fluoro-2-methylindole-1-sulfonyl)-[1,2,4]triazole-1-sulfonamide(WO 2003/053145); methyl3-(4-chlorophenyl)-3-(2-isopropoxycarbonylamino-3-methylbutyrylamino)propanoate(EP-A 1028125);6-(3,4-dichlorophenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,6-(4-tert-butylphenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,5-methyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,5-methyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,6-methyl-5-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,6-ethyl-5-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,5-ethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,5-ethyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,6-octyl-5-propyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,5-methoxymethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,6-octyl-5-trifluoromethyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine and5-trifluoromethyl-6-(3,5,5-trimethylhexyl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamineare known from EP-A 71 792; EP-A 141 317; WO 2003/009687; WO2005/087771; WO 2005/087772; WO 2005/087773; PCT/EP2006/050922; WO2006/087325 and or WO 2006/092428.

N-(2′,4′-difluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-(2′,4′-dichlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-(2′,4′-difluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-(2′,4′-dichlorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-(2′,5′-difluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-(2′,5′-dichlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-(2′,5′-difluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-(2′,5′-dichlorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-(3′,5′-difluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-(3′,5′-dichlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide,N-(3′,5′-difluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-(3′,5′-dichlorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-(3′-fluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-(3′-chlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-(3′-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-(3′-chlorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-(2′-fluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-(2′-chlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-(2′-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-(2′-chlorbiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-(2′-fluoro-4′-chloro-5′-methylbiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-(3′,4′,5′-trifluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-(3′,4′,5′-trifluorobiphenyl-2-yl)-1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide;N-(2′,4′,5′-trifluorobiphenyl-2-yl)-1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide;N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-chlorofluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-[2-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-[2-(1,1,2,3,3,3-hexafluoropropoxy)-phenyl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide,N-[2-(2-chloro-1,1,2-trifluoroethoxy)phenyl]-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-[2-(2-chlor-1,1,2-trifluoroethoxy)phenyl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;4-carbonsäure-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide;N-(4′-(trifluoromethylthio)biphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide;andN-(4′-(trifluoromethylthio)biphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamideare known from WO 2006/087343, WO 2001/42223, WO 2005/34628, WO2005/123689, WO 2005/123690, WO 2006/120219, WO 2007/017450 and/or EPApplication No. 06123463.9.

It is an object of the present invention, with a view to reducing theapplication rates and broadening the activity spectrum of the knowncompounds, to provide mixtures which, at a reduced total amount ofactive compounds applied, have improved activity against pests.

One typical problem arising in the field of pest control lies in theneed to reduce the dosage rates of the active ingredient in order toreduce or avoid unfavorable environmental or toxicological effectswhilst still allowing effective pest control.

In regard to the instant invention the term pests embrace animal pests,and harmful fungi.

Another problem encountered concerns the need to have available pestcontrol agents which are effective against a broad spectrum of pests.

There also exists the need for pest control agents that combineknock-down activity with prolonged control, that is, fast action withlong lasting action.

Another difficulty in relation to the use of pesticides is that therepeated and exclusive application of an individual pesticidal compoundleads in many cases to a rapid selection of pests, that means animalpests, and harmful fungi, which have developed natural or adaptedresistance against the active compound in question. Therefore there is aneed for pest control agents that help prevent or overcome resistance.

It was therefore an object of the present invention to providepesticidal mixtures which solve the problems of reducing the dosage rateand/or enhancing the spectrum of activity and/or combining knock-downactivity with prolonged control and/or to resistance management.

We have found that this object is in part or in whole achieved by thecombination of active compounds defined at the outset. Moreover, we havefound that simultaneous, that is joint or separate, application of acompound I and one or more compounds II or successive application of acompound I and one or more compounds II allows enhanced control ofpests, that means animal pests, and harmful fungi, compared to thecontrol rates that are possible with the individual compounds(synergistic mixtures).

In the definitions of the symbols given in formula I, collective termswere used which are generally representative for the followingsubstituents:

alkyl: saturated straight-chain or branched hydrocarbon radicals having1 to 6, preferably up to 4 carbon atoms, for example C₁-C₄-alkyl, suchas methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl,2-methylpropyl, 1,1-dimethylethyl.

The formula I represents in particular compounds in which R is methyl,ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, or tert. butyl.

The formula I represents in particular compounds in which B¹ is chloroor cyano.

The formula I represents in particular compounds in which B² is bromo.

One embodiment represents compounds of formula I wherein R is hydrogen.Another embodiment represents compounds of formula I wherein R isC₁-C₄-alkyl, particularly methyl.

In particular with a view to their use in the mixtures according to theinvention, preference is given to the compounds I compiled in the tablebelow.

TABLE I No. B¹ B² R I-1 H Br CH₃ I-2 CN Br CH₃ I-3 Cl Br CH₃ I-4 H CF₃CH₃ I-5 CN CF₃ CH₃ I-6 Cl CF₃ CH₃ I-7 H Br H I-8 CN Br H I-9 Cl Br HI-10 H CF₃ H I-11 CN CF₃ H I-12 Cl CF₃ H I-13 H Br CH₂CH₃ I-14 CN BrCH₂CH₃ I-15 Cl Br CH₂CH₃ I-16 H CF₃ CH₂CH₃ I-17 CN CF₃ CH₂CH₃ I-18 ClCF₃ CH₂CH₃ I-19 H Br CH₂CH₂CH₃ I-20 CN Br CH₂CH₂CH₃ I-21 Cl Br CH₂CH₂CH₃I-22 H CF₃ CH₂CH₂CH₃ I-23 CN CF₃ CH₂CH₂CH₃ I-24 Cl CF₃ CH₂CH₂CH₃ I-25 HBr CH(CH₃)₂ I-26 CN Br CH(CH₃)₂ I-27 Cl Br CH(CH₃)₂ I-28 H CF₃ CH(CH₃)₂I-29 CN CF₃ CH(CH₃)₂ I-30 Cl CF₃ CH(CH₃)₂

Particular preference is given to the combinations of the compounds I-2,or I-3 with any one of the compounds II as defined at the outset.Especially preferred is the compound I-3,3-bromo-4′-chloro-1-(3-chloro-2-pyridyl)-2′-methyl-6′-(methylcarbamoyl)pyrazole-5-carboxanilide,with the provisional ISO name chlorantraniliprole.

A preferred embodiment of the invention provides mixtures of a compoundI, in particular of any one of compounds I-2, and I-3 with a compoundII, which is selected from furametpyr, amisulbrom and diclomezine.

Another preferred embodiment of the invention provides mixtures ofcarpropamid with any one of the compounds of formula I compiled in tableI.

Another preferred embodiment of the invention provides mixtures offurametpyr with any one of the compounds of formula I compiled in tableI.

Another preferred embodiment of the invention provides mixtures ofthiadinil with any one of the compounds of formula I compiled in tableI.

Another preferred embodiment of the invention provides mixtures ofN-(3′,4′-dichloro-5-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamidewith any one of the compounds of formula I compiled in table I.

Another preferred embodiment of the invention provides mixtures ofN-(3′,4′,5′-trifluoro-biphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamidewith any one of the compounds of formula I compiled in table I.

Another preferred embodiment of the invention provides mixtures ofN-(3′,4′,5′-trifluoro-biphenyl-2-yl)-1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamidewith any one of the compounds of formula I compiled in table I.

Another preferred embodiment of the invention provides mixtures ofN-(2′,4′,5′-trifluoro-biphenyl-2-yl)-1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamidewith any one of the compounds of formula I compiled in table I.

Another preferred embodiment of the invention provides mixtures ofN-(3′,4′,5′-trifluoro-biphenyl-2-yl)-3-chlorofluoromethyl-1-methyl-1H-pyrazole-4-carboxamidewith any one of the compounds of formula I compiled in table I.

Another preferred embodiment of the invention provides mixtures ofN-[2-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamidewith any one of the compounds of formula I compiled in table I.

Another preferred embodiment of the invention provides mixtures ofN-[2-(1,1,2,3,3,3-hexafluoropropoxy)-phenyl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamidewith any one of the compounds of formula I compiled in table I.

Another preferred embodiment of the invention provides mixtures ofN-[2-(1,1,2,2-tetra-fluoroethoxy)phenyl]-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamidewith any one of the compounds of formula I compiled in table I.

Another preferred embodiment of the invention provides mixtures ofN-(4′-(trifluoro-methylthio)biphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamidewith any one of the compounds of formula I compiled in table I.

Another preferred embodiment of the invention provides mixtures ofN-(4′-(trifluoro-methylthio)biphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamidewith any one of the compounds of formula I compiled in table I.

Another preferred embodiment of the invention provides mixtures of5-fluoro-1,3-di-methyl-1H-pyrazole-4-carboxylic acid[2-(1,2-dimethyl-propyl)-phenyl]-amide, with any one of the compounds offormula I compiled in table I.

Another preferred embodiment of the invention provides mixtures of5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidinewith any one of the compounds of formula I compiled in table I.

Another preferred embodiment of the invention provides mixtures of6-(3,4-dichlorophenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylaminewith any one of the compounds of formula I compiled in table I.

Another preferred embodiment of the invention provides mixtures of6-(4-tert-butyl-phenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylaminewith any one of the compounds of formula I compiled in table I.

Another preferred embodiment of the invention provides mixtures of5-methyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylaminewith any one of the compounds of formula I compiled in table I.

Another preferred embodiment of the invention provides mixtures of5-methyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine with any oneof the compounds of formula I compiled in table I.

Another preferred embodiment of the invention provides mixtures of6-methyl-5-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine with any oneof the compounds of formula I compiled in table I.

Another preferred embodiment of the invention provides mixtures of6-ethyl-5-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine with any oneof the compounds of formula I compiled in table I.

Another preferred embodiment of the invention provides mixtures of5-ethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine with any oneof the compounds of formula I compiled in table I.

Another preferred embodiment of the invention provides mixtures of5-ethyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylaminewith any one of the compounds of formula I compiled in table I.

Another preferred embodiment of the invention provides mixtures of6-octyl-5-propyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine with any oneof the compounds of formula I compiled in table I.

Another preferred embodiment of the invention provides mixtures of5-methoxymethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine withany one of the compounds of formula I compiled in table I.

Another preferred embodiment of the invention provides mixtures of6-octyl-5-trifluoromethyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylaminewith any one of the compounds of formula I compiled in table I.

Another preferred embodiment of the invention provides mixtures of5-trifluoromethyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylaminewith any one of the compounds of formula I compiled in table I.

For use according to the present invention, the mixtures according tothe invention, or a compound I and an active compound II, can beconverted into the customary formulations, for example solutions,emulsions, suspensions, dusts, powders, pastes and granules. The useform depends on the particular intended purpose; in each case, it shouldensure a fine and even distribution of the compound according to theinvention.

The formulations are prepared in a known manner, for example byextending the active compound with solvents and/or carriers, if desiredusing emulsifiers and dispersants. Solvents/auxiliaries which aresuitable are essentially:

-   -   water, aromatic solvents (for example Solvesso products,        xylene), paraffins (for example mineral oil fractions), alcohols        (for example methanol, butanol, pentanol, benzyl alcohol),        ketones (for example cyclohexanone, gamma-butyrolactone),        pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols,        fatty acid dimethyl-amides, fatty acids and fatty acid esters.        In principle, solvent mixtures may also be used,    -   carriers such as ground natural minerals (for example kaolins,        clays, talc, chalk) and ground synthetic minerals (for example        highly disperse silica, silicates); emulsifiers such as nonionic        and anionic emulsifiers (for example polyoxyethylene fatty        alcohol ethers, alkylsulfonates and arylsulfonates) and        dispersants such as lignosulfite waste liquors and        methylcellulose.

Suitable surfactants are alkali metal, alkaline earth metal and ammoniumsalts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonicacid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkylsulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids andsulfated fatty alcohol glycol ethers, furthermore condensates ofsulfonated naphthalene and naphthalene derivatives with formaldehyde,condensates of naphthalene or of naphthalenesulfonic acid with phenoland formaldehyde, polyoxyethylene octylphenol ethers, ethoxylatedisooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers,tributylphenyl polyglycol ethers, tristearylphenyl polyglycol ethers,alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxidecondensates, ethoxylated castor oil, polyoxyethylene alkyl ethers,ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal,sorbitol esters, lignosulfite waste liquors and methylcellulose.

Suitable for the preparation of directly sprayable solutions, emulsions,pastes or oil dispersions are mineral oil fractions of medium to highboiling point, such as kerosene or diesel oil, furthermore coal tar oilsand oils of vegetable or animal origin, aliphatic, cyclic and aromatichydrocarbons, for example toluene, xylene, paraffin,tetrahydronaphthalene, alkylated naphthalenes or their derivatives,methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone,isophorone, strongly polar solvents, for example dimethyl sulfoxide,N-methylpyrrolidone and water.

Also anti-freezing agents such as glycerin, ethylene glycol, propyleneglycol and bactericides such as can be added to the formulation.

Suitable antifoaming agents are for example antifoaming agents based onsilicon or magnesium stearate.

Suitable preservatives are for example Dichlorophen andenzylalkoholhemiformal. Seed Treatment formulations may additionallycomprise binders and optionally colorants.

Binders can be added to improve the adhesion of the active materials onthe seeds after treatment. Suitable binders are block copolymers EO/POsurfactants but also polyvinylalcoholsl, polyvinylpyrrolidones,polyacrylates, polymethacrylates, polybutenes, polyisoutylenes,polystyrene, polyethyleneamines, polyethyleneamides, polyethyleneimines(Lupasol®, Polymin®), polyethers, polyurethans, polyvinylacetate, tyloseand copolymers derived from these polymers.

Optionally, also colorants can be included in the formulation. Suitablecolorants or dyes for seed treatment formulations are Rhodamin B, C.I.Pigment Red 112, C.I. Solvent Red 1, pigment blue 15:4, pigment blue15:3, pigment blue 15:2, pigment blue 15:1, pigment blue 80, pigmentyellow 1, pigment yellow 13, pigment red 112, pigment red 48:2, pigmentred 48:1, pigment red 57:1, pigment red 53:1, pigment orange 43, pigmentorange 34, pigment orange 5, pigment green 36, pigment green 7, pigmentwhite 6, pigment brown 25, basic violet 10, basic violet 49, acid red51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10,basic red 108.

Examples of a gelling agent is carrageen (Satiagel®)

Powders, materials for spreading and dustable products can be preparedby mixing or concomitantly grinding the active substances with a solidcarrier.

Granules, for example coated granules, impregnated granules andhomogeneous granules, can be prepared by binding the active compounds tosolid carriers. Examples of solid carriers are mineral earths such assilica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk,bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate,magnesium sulfate, magnesium oxide, ground synthetic materials,fertilizers, such as, for example, ammonium sulfate, ammonium phosphate,ammonium nitrate, ureas, and products of vegetable origin, such ascereal meal, tree bark meal, wood meal and nutshell meal, cellulosepowders and other solid carriers.

In general, the formulations comprise from 0.01 to 95% by weight,preferably from 0.1 to 90% by weight, of the active compound. The activecompounds are employed in a purity of from 90% to 100%, preferably 95%to 100% (according to NMR spectrum).

For seed treatment purposes, respective formulations can be diluted 2-10fold leading to concentrations in the ready to use preparations of 0.01to 60% by weight active compound by weight, preferably 0.1 to 40% byweight.

The following are examples of formulations: 1. Products for dilutionwith water For seed treatment purposes, such products may be applied tothe seed diluted or undiluted.

A Water-Soluble Concentrates (SL, LS)

10 parts by weight of the active compounds are dissolved with 90 partsby weight of water or a water-soluble solvent. As an alternative,wetters or other auxiliaries are added. The active compound dissolvesupon dilution with water. A formulation having an active compoundcontent of 10% by weight is obtained in this manner.

B Dispersible Concentrates (DC)

20 parts by weight of the active compounds are dissolved in 70 parts byweight of cyclohexanone with addition of 10 parts by weight of adispersant, for example polyvinylpyrrolidone. Dilution with water givesa dispersion. The active compound content is 20% by weight.

C Emulsifiable Concentrates (EC)

15 parts by weight of the active compounds are dissolved in 75 parts byweight of xylene with addition of calcium dodecylbenzenesulfonate andcastor oil ethoxylate (in each case 5 parts by weight). Dilution withwater gives an emulsion. The formulation has an active compound contentof 15% by weight.

D Emulsions (EW, EO, ES)

25 parts by weight of the active compounds are dissolved in 35 parts byweight of xylene with addition of calcium dodecylbenzenesulfonate andcastor oil ethoxylate (in each case 5 parts by weight). This mixture isadded into 30 parts by weight of water by means of an emulsifyingmachine (e.g. Ultraturrax) and made into a homogeneous emulsion.Dilution with water gives an emulsion. The formulation has an activecompound content of 25% by weight.

E Suspensions (SC, OD, FS)

In an agitated ball mill, 20 parts by weight of the active compounds arecomminuted with addition of 10 parts by weight of dispersants andwetters and 70 parts by weight of water or an organic solvent to give afine active compound suspension. Dilution with water gives a stablesuspension of the active compound. The active compound content in theformulation is 20% by weight.

F Water-Dispersible Granules and Water-Soluble Granules (WG, SG)

50 parts by weight of the active compounds are ground finely withaddition of 50 parts by weight of dispersants and wetters and made intowater-dispersible or water-soluble granules by means of technicalappliances (for example extrusion, spray tower, fluidized bed). Dilutionwith water gives a stable dispersion or solution of the active compound.The formulation has an active compound content of 50% by weight.

G Water-Dispersible Powders and Water-Soluble Powders (WP, SP, SS, WS)

75 parts by weight of the active compounds are ground in a rotor-statormill with addition of 25 parts by weight of dispersants and wetters aswell as silica gel. Dilution with water gives a stable dispersion orsolution of the active compound. The active compound content of theformulation is 75% by weight.

H Gel Formulations (GF)

In a ball mill, 20 parts by weight of the active compounds, 10 parts byweight of dispersant, 1 part by weight of gelling agent and 70 parts byweight of water or an organic solvent are ground to give a finesuspension. On dilution with water, a stable suspension having an activecompound content of 20% by weight is obtained.

2. Products to be Applied Undiluted

I Dustable Powders (DP, DS)

5 parts by weight of the active compounds are ground finely and mixedintimately with 95 parts by weight of finely divided kaolin. This givesa dustable product having an active compound content of 5% by weight.

J Granules (GR, FG, GG, MG)

0.5 part by weight of the active compounds is ground finely andassociated with 99.5 parts by weight of carriers. Current methods areextrusion, spray-drying or the fluidized bed. This gives granules to beapplied undiluted having an active compound content of 0.5% by weight.

K ULV Solutions (UL)

10 parts by weight of the active compounds are dissolved in 90 parts byweight of an organic solvent, for example xylene. This gives a productto be applied undiluted having an active compound content of 10% byweight.

For seed treatment, use is usually made of water-soluble concentrates(LS), suspensions (FS), dustable powders (DS), water-dispersible andwater-soluble powders (WS, SS), emulsions (ES), emulsifiableconcentrates (EC) and gel formulations (GF). These formulations can beapplied to the seed in undiluted form or, preferably, diluted.Application can be carried out prior to sowing.

In a preferred embodiment a FS formulation is used for seed treatment.Typically, a FS formulation may comprise 1-800 g/l of active ingredient,1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l ofbinder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent,preferably water.

The active compounds can be used as such, in the form of theirformulations or the use forms prepared therefrom, for example in theform of directly sprayable solutions, powders, suspensions ordispersions, emulsions, oil dispersions, pastes, dustable products,materials for spreading, or granules, by means of spraying, atomizing,dusting, spreading or pouring. The use forms depend entirely on theintended purposes; the intention is to ensure in each case the finestpossible distribution of the active compounds according to theinvention.

Aqueous use forms can be prepared from emulsion concentrates, pastes orwettable powders (sprayable powders, oil dispersions) by adding water.To prepare emulsions, pastes or oil dispersions, the substances, as suchor dissolved in an oil or solvent, can be homogenized in water by meansof a wetter, tackifier, dispersant or emulsifier.

Alternatively, it is possible to prepare concentrates composed of activesubstance, wetter, tackifier, dispersant or emulsifier and, ifappropriate, solvent or oil, and such concentrates are suitable fordilution with water.

The active compound concentrations in the ready-to-use preparations canbe varied within relatively wide ranges. In general, they are from0.0001 to 10%, preferably from 0.01 to 1%.

The active compounds may also be used successfully in theultra-low-volume process (ULV), by which it is possible to applyformulations comprising over 95% by weight of active compound, or evento apply the active compound without additives.

Various types of oils, wetters, adjuvants, herbicides, fungicides, otherpesticides, or bactericides may be added to the active compounds, ifappropriate not until immediately prior to use (tank mix). These agentscan be admixed with the agents according to the invention in a weightratio of 1:100 to 100:1, preferably 1:10 to 10:1.

Compositions of this invention may also contain other activeingredients, for example other pesticides, herbicides, fertilizers suchas ammonium nitrate, urea, potash, and superphosphate, phytotoxicantsand plant growth regulators and safeners. These additional ingredientsmay be used sequentially or in combination with the above-describedcompositions, if appropriate also added only immediately prior to use(tank mix). For example, the plant(s) may be sprayed with a compositionof this invention either before or after being treated with other activeingredients.

The compound I and the compound II can be applied in a weight ratio offrom 5000:1 to 1:5000, preferably from 500:1 to 1:100, more preferablyfrom 100:1 to 1:100, in particular from 20:1 to 1:20, most preferredfrom 10:1 to 1:10.

When preparing the mixtures, it is preferred to employ the pure activecompounds I and II, to which further active compounds against harmfulfungi or against other pests, such as insects, arachnids or nematodes,or else herbicidal or growth-regulating active compounds or fertilizerscan be added as further active components according to need.

Usually, mixtures of a compound I with an active compound II areemployed. However, in certain cases mixtures of the compound I with twoor, if appropriate, more active components may be advantageous.

Suitable further active components in the above sense are in particularthe active compounds II, mentioned at the outset and in particular thepreferred active compounds mentioned above.

If more than one compound II is used according to the invention, thefurther active components are, if desired, added in a ratio of from 20:1to 1:20 to the compound I.

Alternatively such further active compounds are applied in a weightration from 20:1 to 1:20 to the compound II.

The mixtures of the compounds I and active compounds II are employed bytreating the fungi or the plants, seeds, materials or soil to beprotected from fungal attack with a fungicidally effective amount of theactive compounds. The application can be carried out both before andafter the infection of the materials, plants or seeds by the fungi.

In the method of combating harmful fungi depending on the type ofcompound and the desired effect, the application rates of the mixturesaccording to the invention are from 5 g/ha to 2000 g/ha, preferably from50 to 900 g/ha, in particular from 50 to 750 g/ha.

Correspondingly, the application rates for the compound I are generallyfrom 1 to 1000 g/ha, preferably from 10 to 900 g/ha, in particular from20 to 750 g/ha.

Correspondingly, the application rates for the active compound II aregenerally from 1 to 2000 g/ha, preferably from 10 to 900 g/ha, inparticular from 40 to 500 g/ha.

The method for controlling harmful fungi is carried out by the separateor joint application of a compound I and the active compound II or themixtures of the compound I and the active compound II by spraying ordusting the seeds, the plants or the soil before or after sowing of theplants or before or after emergence of the plants.

The treatment can be made into the seedbox before planting into thefield.

The mixtures of a compound I and at least a compound II or thesimultaneous, that is joint or separate, use of a compound I and atleast a compound II are distinguished by being highly active against awide range of phytopathogenic fungi, in particular from the classes ofthe Ascomycetes, Deuteromycetes, Peronosporomycetes and Basidiomycetes.Some of them act systemically and can be used in crop protection asfoliar fungicides, as fungicides for seed dressing and as soil-actingfungicides.

They are particularly important for controlling a multitude of fungi onvarious cultivated plants, such as bananas, cotton, vegetable species(for example cucumbers, beans and cucurbits), barley, grass, oats,coffee, potatoes, corn, fruit species, rice, rye, soya, tomatoes,grapevines, wheat, ornamental plants, sugar cane and also on a largenumber of seeds.

The compounds I and the compounds II can be applied simultaneously, thatis jointly or separately, or in succession, the sequence, in the case ofseparate application, generally not having any effect on the result ofthe control measures.

They are particularly important in the control of a multitude of fungion various cultivated plants, such as wheat, rye, barley, oats, rice,corn, grass, bananas, cotton, soybeans, coffee, sugar cane, vines,fruits and ornamental plants, and vegetables, such as cucumbers, beans,tomatoes, potatoes and cucurbits, and on the seeds of these plants. Theycan also be used in crops which are tolerant to insect or fungal attackbecause of breeding, including genetic engineering methods. Moreover,they are suitable for controlling Botryosphaeria species, Cylindrocarponspecies, Eutypa lata, Neonectria liriodendri and Stereum hirsutum whichinfest inter alia the wood or the roots of grapevines.

They are especially suitable for controlling each of the following plantdiseases:

Alternaria species on vegetables, rapeseed, sugar beet, fruit, rice,soybeans and on potatoes (for example A. solani or A. alternata) andtomatoes (for example A. solani or A. alternata) and Alternaria ssp.(black head mold) on wheat,

Aphanomyces species on sugar beet and vegetables,

Ascochyta species on cereals and vegetables, for example Ascochytatritici (leaf spot) on wheat,

Bipolaris and Drechslera species on corn (for example, D. maydis),cereals, rice and lawn,

Blumeria graminis (powdery mildew) on cereals (for example wheat orbarley),

Botrytis cinerea (gray mold) on strawberries, vegetables, flowers,grapevines and wheat (head mold),

Bremia lactucae on lettuce,

Cercospora species on corn, rice, sugar beet, and e.g. Cercospora sojina(leaf spot) or Cercospora kikuchii (leaf spot) on soybeans,

Cladosporium herbarum (ear rot) on wheat,

Cochliobolus species on corn, cereals (e.g. Cochliobolus sativus) andrice (e.g. Cochliobolus miyabeanus),

Colletotricum species on cotton and e.g. Colletotrichum truncatum(anthracnose) on soybeans,

Corynespora cassiicola (leaf spot) on soybeans,

Dematophora necatrix (root/stem rot) on soybeans,

Diaporthe phaseolorum (stem disease) on soybeans,

Drechslera species, Pyrenophora species on corn, cereals, rice and lawn,on barley (for example, D. teres) or on wheat (for example D.tritici-repentis),

Esca on grapevines, caused by Phaeoacremonium chlamydosporium, Ph.Aleophilum, and Formitipora punctata (syn. Phellinus punctatus),

Elsinoe empelina on grapevines,

Epicoccum spp. (black head mold) on wheat,

Exserohilum species on corn,

Erysiphe cichoracearum and Sphaerotheca fuliginea on cucumbers,

Fusarium and Verticillium species on various plants: for example, F.graminearum or F. culmorum (root rot) on cereals (for example wheat orbarley) or for example F. oxysporum on tomatoes,

and Fusarium solani (stem disease) on soybeans,

Gaeumanomyces graminis (root black) on cereals (for example wheat orbarley),

Gibberella species on cereals and rice (for example Gibberellafujikuroi),

Glomerella cingulata on grapevines and other plants,

Grainstaining complex on rice,

Guignardia budwelli on grapevines,

Helminthosporium species on corn and rice,

Isariopsis clavispora on grapevines,

Macrophomina phaseolina (root/stem rot) on soybeans,

Michrodochium nivale (snow mold) on cereals (for example wheat orbarley),

Microsphaera difusa (powdery mildew) on soybeans,

Mycosphaerella species on cereals, bananas and peanuts, such as, forexample, M. graminicola on wheat or M. fijiensis on bananas,

Peronospora species on cabbage (for example P. brassicae), onions, (forexample, P. destructor) and for example Peronospora manshurica (downymildew) on soybeans,

Phakopsara pachyrhizi (soybean rust) and Phakopsara meibomiae (soybeanrust) on soybeans,

Phialophora gregata (stem disease) on soybeans,

Phomopsis species on sunflowers, grapevines (for example P. viticola)and soybeans (for example Phomopsis phaseo),

Phytophthora species on various plants, for example P. capsicion bellpepper, Phytopthora megasperma (leaf/stem rot) on soybeans, Phytophthorainfestans on potatoes and tomatoes,

Plasmopara viticola on grapevines,

Podosphaera leucotricha on apples,

Pseudocercosporella herpotrichoides (eyespot) on cereals (wheat orbarley),

Pseudoperonospora on various plants, for example P. cubensis on cucumberor P. humili on hops,

Pseudopezicula tracheiphilai on grapevines,

Puccinia species on various plants, for example P. triticina, P.striformins, P. hordei or P. graminis on cereals (for example wheat orbarley) or on asparagus (for example P. asparagi),

Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S.attenuatum, Pyrenophora tritici-repentis (leaf spot) on wheat orPyrenophora teres (net spot) on barley, Entyloma oryzae on rice,

Pyricularia grisea on lawn and cereals,

Pythium spp. on lawn, rice, corn, wheat, cotton, oilseed rape,sunflowers, sugar beet, vegetables and other plants (for example P.ultiumum or P. aphanidermatum),

Ramularia collo-cygni (Ramularia/sunburn complex/physiological leafspots) on barley,

Rhizoctonia species on cotton, rice, potatoes, lawn, corn, oilseed rape,potatoes, sugar beet, vegetables and on various other plants, forexample Rhizoctonia solani (root/stem rot) on soybeans or Rhizoctoniacerealis (sharp eyespot) on wheat or barley,

Rhynchosporium secalis on barley (leaf spot), rye and triticale,

Scierotinia species on oilseed rape, sunflowers and, for exampleScierotinia scerotiorum (stem disease) or Scierotinia rolfsii (stemdisease) on soybeans,

Septoria glycines (leaf spot) on soybeans,

Septoria tritici (leaf septoria) and Stagonospora nodorum on wheat,

Erysiphe (syn. Uncinula) necator on grapevines,

Setospaeria species on corn and lawn,

Sphacelotheca reilinia on corn,

Stagonospora nodorum (ear septoria) on wheat,

Thievaliopsis species on soybeans and cotton,

Tilletia species on cereals,

Typhula incarnata (snow rot) on wheat or barley,

Ustilago species on cereals, corn (for example U. maydis) and sugarcane,

Venturia species (scab) on apples (for example V. inaequalis) and pears.

The target crops may be crops of conventional plants or crops ofgenetically modified plants (“GM plants” or “GMOs”).

The compositions according to the invention are therefore also suitablefor use in herbicide-resistant, pest-resistant and/or fungus-resistanttransgenic crops of useful plants, especially cereals, cotton, soybeans,sugar beet, sugar cane, plantation crops (e.g. citrus fruits, coffee,bananas), rape, maize and rice.

Herbicide-resistant crops are to be understood as including those thathave been made tolerant to herbicides or classes of herbicides (e.g.ALS-, GS-, EPSPS-, PPO- and HPPD-inhibitors) by means of conventionalbreeding or genetic engineering methods. An example of a crop that hasbeen made tolerant by conventional breeding methods to, for example,imidazolinones such as imazamox is Clearfield® summer rape (canola).Examples of crops made tolerant to herbicides by genetic engineeringmethods are maize varieties resistant to, for example, glyphosate orglufosinate, which are commercially available under the trade namesRoundupReady® and LibertyLink®, respectively.

In the context of the present invention, pest-resistant and/orfungus-resistant transgenic useful plants are expressly understood toinclude those useful plants which, in addition to having the pestresistance and/or fungus resistance, also have herbicide tolerance.Among the group of herbicide-tolerant useful plants preference is given,in accordance with the invention, to useful plants having tolerance withrespect to glyphosate, glufosinate-ammonium, ALS (acetolactate synthase)inhibitors, such as sulfonylureas, e.g. primisulfuron, prosulfuron andtrifloxysulfuron, or bromoxynil, such as, for example, Bt11 maize orHerculex I® maize.

Pest-resistant transgenic crop plants are to be understood in thecontext of the present invention as being plants which have been sotransformed by the use of recombinant DNA techniques that they arecapable of synthesising one or more selectively acting toxins, such asare known, for example, from toxin-producing bacteria, especially thoseof the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, forexample, insecticidal proteins, e.g. insecticidal proteins from Bacilluscereus or Bacillus popliae; or insecticidal proteins from Bacillusthuringiensis, such as alpha-endotoxins, e.g. CryIA(b), CryIA(c), CryIF,CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(bi) or Cry9c, or vegetativeinsecticidal proteins (VIP), e.g. VIP1, VIP2, VIP3 or VIP3A; orinsecticidal proteins of bacteria that colonise nematodes, for examplePhotorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens,Xenorhabdus nematophilus, toxins produced by animals, such as scorpiontoxins, arachnid toxins, wasp toxins and other insect-specificneurotoxins; toxins produced by fungi, such as Streptomycetes toxins;plant lectins, such as pea lectins, barley lectins or snowdrop lectins;agglutinins; proteinase inhibitors, such as trypsin inhibitors, serineprotease inhibitors, patatin, cystatin, papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroid-oxidase, ecdysteroid-UDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ionchannel blockers, such as blockers of sodium or calcium channels,juvenile hormone esterase, diuretic hormone receptors, stilbenesynthase, bibenzyl synthase, chitinases and glucanases.

In the context of the present invention there are to be understood byd-endotoxins, for example CryIA(b), CryIA(c), CryIF, CryIF(a2),CryIIA(b), CryIIIA, CryIIIB(bi) or Cry9c, or vegetative insecticidalproteins (VIP), for example VIP1, VIP2, VIP3 or VIP3A, expressly alsohybrid toxins, truncated toxins and modified toxins. Hybrid toxins areproduced recombinantly by a new combination of different domains ofthose proteins (see, for example, WO 02/15701). An example of atruncated toxin is a truncated CryIA(b), which is expressed in Bt11maize of Syngenta Seeds SAS, as described hereinbelow. In the case ofmodified toxins, one or more amino acids of the naturally occurringtoxin is/are replaced. In such amino acid replacements, preferablynon-naturally present protease recognition sequences are inserted intothe toxin, such as, for example, in the case of CryIIIA055, acathepsin-D-recognition sequence is inserted into a CryIIIA toxin (seeWO 03/018810).

Examples of such toxins or transgenic plants capable of synthesisingsuch toxins are disclosed, for example, in EP-A 374 753, WO 93/07278, WO95/34656, EP-A 427 529, EP-A 451 878 and WO 03/052073.

The processes for the production of such transgenic plants are generallyknown to the person skilled in the art and are described, for example,in the publications mentioned above. CryI-type deoxyribonucleic acidsand their preparation are known, for example, from WO 95/34656, EP-A 367474, EP-A 401 979 and WO 90/13651.

The toxin contained in the transgenic plants provides the plants withtolerance to harmful insects. Such insects can occur in any taxonomicgroup of insects, but are especially commonly found in beetles(Coleoptera), two-winged insects (Diptera) and butterflies(Lepidoptera).

The following harmful insects from different taxonomic groups areespecially common in maize crops:

Ostrinia nubilalis, European corn borer,

Agrotis ipsilon, black cutworm,

Helicoverpa zea, corn earworm,

Spodoptera frugiperda, fall armyworm,

Diatraea grandiosella, southwestern corn borer,

Elasmopalpus lignosellus, lesser cornstalk borer,

Diatraea saccharalis, sugarcane borer,

Diabrotica virgifera virgifera, western corn rootworm,

Diabrotica longicornis barberi, northern corn rootworm,

Diabrotica undecimpunctata howardi, southern corn rootworm,

Melanotus spp., wireworms,

Cyclocephala borealis, northern masked chafer (white grub),

Cyclocephala immaculata, southern masked chafer (white grub),

Popillia japonica, Japanese beetle,

Chaetocnema pulicaria, corn flea beetle,

Sphenophorus maidis, maize billbug,

Rhopalosiphum maidis, corn leaf aphid,

Anuraphis maidiradicis, corn root aphid,

Blissus leucopterus leucopterus, chinch bug,

Melanoplus femurrubrum, red-legged grasshopper,

Melanoplus sanguinipes, migratory grasshopper,

Hylemya platura, seedcom maggot,

Agromyza parvicornis, corn blotch leafminer,

Anaphothrips obscurus, grass thrips,

Solenopsis milesta, thief ant,

Tetranychus urticae, two-spotted spider mite.

Transgenic plants containing one or more genes that code for aninsecticidal resistance and express one or more toxins are known andsome of them are commercially available. Examples of such plants are:YieldGard® (maize variety that expresses a CryIA(b) toxin); YieldGardRootworm® (maize variety that expresses a CryIIIB(bi) toxin); YieldGardPlus® (maize variety that expresses a CryIA(b) and a CryIIIB(bi) toxin);Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I®(maize variety that expresses a CryIF(a2) toxin and the enzymephosphinothricin N-acetyl-transferase (PAT) to achieve tolerance to theherbicide glufosinate ammonium); NuCOTN 33B® (cotton variety thatexpresses a CryIA(c) toxin); Bollgard I® (cotton variety that expressesa CryIA(c) toxin); Bollgard II® (cotton variety that expresses aCryIA(c) and a CryIIA(b) toxin); VIPCOT® (cotton variety that expressesa VIP toxin); NewLeaf® (potato variety that expresses a CryIIIA toxin);NatureGard® and Protecta®.

Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a truncated CryIA(b) toxin. Bt11 maize alsotransgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nuhilalis and Sesamia nonagrioides) bytransgenic expression of a CryIA(b) toxin. Bt176 maize alsotransgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Maize which hasbeen rendered insect-resistant by transgenic expression of a modifiedCryIHA toxin. This toxin is Cry3A055 modified by insertion of acathepsin-D-protease recognition sequence. The preparation of suchtransgenic maize plants is described in WO 03/018810.4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863expresses a CryIIIB(bi) toxin and has resistance to certain Coleopterainsects.5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/ES/96/02.6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C/NLJ00/10. Geneticallymodified maize for the expression of the protein Cry1 F for achievingresistance to certain Lepidoptera insects and of the PAT protein forachieving tolerance to the herbicide glufosinate ammonium.7. NK603×MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue deTervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03.Consists of conventionally bred hybrid maize varieties by crossing thegenetically modified varieties NK603 and MON 810. NK603×MON 810 Maizetransgenically expresses the protein CP4 EPSPS, obtained fromAgrobacterium sp. strain CP4, which imparts tolerance to the herbicideRoundup (contains glyphosate), and also a CryIA(b) toxin obtained fromBacillus thuringiensis subsp. kurstaki which brings about tolerance tocertain Lepidoptera, including the European corn borer.

Transgenic crops of insect-resistant plants are also described in BATS(Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS,Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).

In the context of the present invention, fungus-resistant transgeniccrop plants are to be understood as being those which have been sotransformed by the use of recombinant DNA techniques that they arecapable of synthesising antipathogenic substances having a selectiveaction, such as, for example, the so-called “pathogenesis-relatedproteins” (PRPs, see e.g. EP-A 392 225). Examples of such antipathogenicsubstances and transgenic plants capable of synthesising suchantipathogenic substances are known, for example, from EP-A 392 225, WO95/33818 and EP-A 353 191. The methods of producing such transgenicplants are generally known to the person skilled in the art and aredescribed, for example, in the publications mentioned above.

Antipathogenic substances which can be expressed by such transgenicplants include, for example, ion channel blockers, such as blockers forsodium and calcium channels, for example the viral KP1, KP4 or KP6toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases;the so-called “pathogenesis-related proteins” (PRPs; see e.g. EP-A 392225); antipathogenic substances produced by microorganisms, for examplepeptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818)or protein or polypeptide factors involved in plant pathogen defence(so-called “plant disease resistance genes”, as described in WO03/000906). Further areas of use of the compositions according to theinvention are the protection of stored goods and storerooms and theprotection of raw materials, such as wood, textiles, floor coverings orbuildings, and also in the hygiene sector, especially the protection ofhumans, domestic animals and productive livestock against pests of thementioned type.

In the context of the invention transgenic plants may contain one ormore genes that code for an insecticidal resistance as well as for aherbicidal resistance, as described above (e.g. RR Bollguard® or RRYieldguard® traits). Those are considered transgenic plants containing adouble or even triple stacked genes. Furthermore, this concept ofmultiple stacking of genes or events in a transgenic plant can beconsidered also for a broader and larger application, such as fungicidalresistance or drought resistance. The latter are to be understood ofwhich have been so transformed by the use of recombinant DNA techniquesthat they are capable providing stress resistance under droughtselection pressure to the crop plant. Furthermore, genes which increasethe yield potential of a given crop plant per se, when introduced bytransformation technologies with the use of recombinant DNA, providingadditional yield by modifying a given physiological pathway of the cropplant, have to be considered in the multiple stacking concept oftransgenic crop plants, e.g. RR2Yield® in soybean.

The compounds I and II or the mixtures or the corresponding formulationsare applied by treating the harmful fungi, the plants, seeds, soils,areas, materials or spaces to be kept free from them with a fungicidallyeffective amount of the mixture or, in the case of separate application,of the compounds I and II. Application can be carried out before orafter infection by the harmful fungi.

The mixtures of compounds I and II, or the compounds I and II usedsimultaneously, that is jointly or separately, exhibit also outstandingaction against pests from the following orders:

insects from the order of the lepidopterans (Lepidoptera), for exampleAgrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsiagemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius,Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneurafumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydiapomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella,Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella,Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholithafunebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens,Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea,Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria,Laphygma exigua, Leucoptera coffeella, Leucoptera scitella,Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis,Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosomaneustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis,Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalerabucephala, Phthorimaea operculella, Phyllocnistis citrella, Pierisbrassicae, Plathypena scabra, Plutella xylostella, Pseudoplusiaincludens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotrogacerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodopteralittoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrixviridana, Trichoplusia ni and Zeiraphera canadensis,beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus,Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar,Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athoushaemorrhoidalis, Atomaria linearis, Blastophagus piniperda, Blitophagaundata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscusbetulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata,Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis,Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp., Diabroticalongicornis, Diabrotica semipunctata, Diabrotica 12-punctata Diabroticaspeciosa, Diabrotica virgifera, Epilachna varivestis, Epitrixhirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hyperabrunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lemamelanopus, Leptinotarsa decemlineata, Limonius californicus,Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus,Melolontha hippocastan, Melolontha melolontha, Oulema oryzae,Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae,Phyllobius pyri, Phyllotreta chrysocephala, Phyllophaga sp.,Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata,Popillia japonica, Sitona lineatus and Sitophilus granaria,flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedesvexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians,Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anophelesleucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphoravicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax,Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysopsatlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobiaanthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus,Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culisetamelanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Deliaantique, Delia coarctata, Delia platura, Delia radicum, Dermatobiahominis, Fannia canicularis, Geomyza Tripunctata, Gasterophilusintestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes,Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris,Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconopstorrens, Liriomyza sativae, Liriomyza trifoli, Lucilia caprina, Luciliacuprina, Lucilia sericata, Lycoria pectoralis, Mansonia titillanus,Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis,Opomyza florum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua,Phorbia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psorophoracolumbiae, Psila rosae, Psorophora discolor, Prosimulium mixtum,Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis,Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus,Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula oleracea,and Tipula paludosathrips (Thysanoptera), e.g. Dichromothrips corbetti, Dichromothrips ssp,Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici,Scirtothrips citrci, Thrips oryzae, Thrips palmi and Thrips tabactermites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes,Heterotermes aureus, Reticulitermes flavipes, Reticulitermes virginicus,Reticulitermes lucifugus, Termes natalensis, and Coptotermes formosanus,cockroaches (Blattaria—Blattodea), e.g. Battella germanica, Battellaasahinae, Periplaneta americana, Periplaneta japonica, Periplanetabrunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blattaorientalis,true bugs (Hemiptera), e.g. Acrosternum hilare, Blissus leucopterus,Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius,Eurygaster integriceps, Euschistus impictiventris, Leptoglossusphyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesmaquadrata, Solubea insularis, Thyanta perditor, Acyrthosiphon onobrychis,Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphispomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphisspiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani,Bemisia argentifolii, Brachycaudus cardui, Brachycaudus helichrysi,Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae,Capitophorus horni, Cerosipha gossypi, Chaetosiphon fragaefolii,Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphisradicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphispyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae,Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megouraviciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzus persicae,Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri,Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida,Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus,Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum,Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneuralanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxopteraaurantiiand, Viteus vitifolii, Cimex lectularius, Cimex hemipterus,Reduvius senilis, Triatoma spp., and Arilus critatus.ants, bees, wasps, sawflies (Hymenoptera), e.g. Athalia rosae, Attacephalotes, Atta capiguara, Atta cephalotes, Atta laevigata, Attarobusta, Atta sexdens, Atta texana, Crematogaster spp., Hoplocampaminuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsisgeminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni,Pogonomyrmex barbatus, Pogonomyrmex californicus, Pheidole megacephala,Dasymutilla occidentalis, Bombus spp. Vespula squamosa, Paravespulavulgaris, Paravespula pennsylvanica, Paravespula germanica,Dolichovespula maculata, Vespa crabro, Polistes rubiginosa, Camponotusfloridanus, and Linepithema humile,crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica,Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus,Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes,Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana,Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus,Oedaleus senegalensis, Zonozerus variegatus, Hieroglyphus daganensis,Kraussaria angulifera, Calliptamus italicus, Chortoicetes terminifera,and Locustana pardalina,Arachnoidea, such as arachnids (Acarina), e.g. of the familiesArgasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum,Amblyomma variegatum, Ambryomma maculatum, Argas persicus, Boophilusannulatus, Boophilus decoloratus, Boophilus microplus, Dermacentorsilvarum, Dermacentor andersoni, Dermacentor variabilis, Hyalommatruncatum, Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodesholocyclus, Ixodes pacificus, Ornithodorus moubata, Ornithodorus hermsi,Ornithodorus turicata, Ornithonyssus bacoti, Otobius megnini,Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus sanguineus,Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei,and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrataoleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemuspallidus and Polyphagotarsonemus latus, Tenuipalpidae spp. such asBrevipalpus phoenicis; Tetranychidae spp. such as Tetranychuscinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychustelarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, andOligonychus pratensis; Araneida, e.g. Latrodectus mactans, andLoxosceles reclusa,fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis,Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllusfasciatus,silverfish, firebrat (Thysanura), e.g. Lepisma saccharina and Thermobiadomestica,centipedes (Chilopoda), e.g. Scutigera coleoptrata,millipedes (Diplopoda), e.g. Narceus spp.,Earwigs (Dermaptera), e.g. forficula auricularia,lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanuscorporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis,Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthusstramineus and Solenopotes capillatus,plant parasitic nematodes such as root-knot nematodes, Meloidogynearenaria, Meloidogyne chitwoodi, Meloidogyne exigua, Meloidogyne hapla,Meloidogyne incognita, Meloidogyne javanica and other Meloidogynespecies; cyst nematodes, Globodera rostochiensis, Globodera pallida,Globodera tabacum and other Globodera species, Heterodera avenae,Heterodera glycines, Heterodera schachtii, Heterodera trifolii, andother Heterodera species, seed gall nematodes, Anguina funesta, Anguinatritici and other Anguina species; stem and foliar nematodes,Aphelenchoides besseyi, Aphelenchoides fragariae, Aphelenchoidesritzemabosi and other Aphelenchoides species; sting nematodes,Belonolaimus longicaudatus and other Belonolaimus species; pinenematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species,ring nematodes, Criconema species, Criconemella species, Criconemoidesspecies, and Mesocriconema species; stem and bulb nematodes, Ditylenchusdestructor, Ditylenchus dipsaci, Ditylenchus myceliophagus and otherDitylenchus species; awl nematodes, Dolichodorus species; spiralnematodes, Helicotylenchus dihystera, Helicotylenchus multicinctus andother Helicotylenchus species, Rotylenchus robustus and otherRotylenchus species; sheath nematodes, Hemicycliophora species andHemicriconemoides species; Hirshmanniella species, lance nematodes,Hoplolaimus columbus, Hoplolaimus galeatus and other Hoplolaimusspecies, false root-knot nematodes, Nacobbus aberrans and other Nacobbusspecies; needle nematodes, Longidorus elongates and other Longidorusspecies; pin nematodes, Paratylenchus species; lesion nematodes,Pratylenchus brachyurus, Pratylenchus coffeae, Pratylenchus curvitatus,Pratylenchus goodeyi, Pratylencus neglectus, Pratylenchus penetrans,Pratylenchus scribneri, Pratylenchus vulnus, Pratylenchus zeae and otherPratylenchus species, Radinaphelenchus cocophilus and otherRadinaphelenchus species; burrowing nematodes, Radopholus similis andother Radopholus species; reniform nematodes, Rotylenchulus reniformisand other Rotylenchulus species, Scutellonema species, stubby rootnematodes, Trichodorus primitivus and other Trichodorus species;Paratrichodorus minor and other Paratrichodorus species; stuntnematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and otherTylenchorhynchus species and Merlinius species, citrus nematodes,Tylenchulus semipenetrans and other Tylenchulus species, daggernematodes, Xiphinema americanum, Xiphinema index, Xiphinemadiversicaudatum and other Xiphinema species; and other plant parasiticnematode species.

Moreover, the inventive mixtures are especially useful for the controlof Lepidoptera, Coleoptera, Diptera, Thysanoptera and Hymenoptera.

Moreover, the inventive mixtures are especially useful for the controlof non-crop pests (household, turf, ornamental).

The mixtures according to the invention can be applied to any and alldevelopmental stages of pests, such as egg, larva, pupa, and adult. Thepests may be controlled by contacting the target pest, its food supply,habitat, breeding ground or its locus with a pesticidally effectiveamount of the inventive mixtures or of compositions comprising themixtures.

“Locus” means a plant, seed, soil, area, material or environment inwhich a pest is growing or may grow.

In general, “pesticidally effective amount” means the amount of theinventive mixtures or of compositions comprising the mixtures needed toachieve an observable effect on growth, including the effects ofnecrosis, death, retardation, prevention, and removal, destruction, orotherwise diminishing the occurrence and activity of the targetorganism. The pesticidally effective amount can vary for the variousmixtures/compositions used in the invention. A pesticidally effectiveamount of the mixtures/compositions will also vary according to theprevailing conditions such as desired pesticidal effect and duration,weather, target species, locus, mode of application, and the like.

The inventive mixtures or compositions of these mixtures can also beemployed for protecting plants from attack or infestation by insects,acarids or nematodes comprising contacting a plant, or soil or water inwhich the plant is growing.

In the context of the present invention, the term plant refers to anentire plant, a part of the plant or the propagation material of theplant, that is, the seed or the seedling.

Plants which can be treated with the inventive mixtures include allgenetically modified plants or transgenic plants, e.g. crops whichtolerate the action of herbicides or fungicides or insecticides owing tobreeding, including genetic engineering methods, or plants which havemodified characteristics in comparison with existing plants, which canbe generated for example by traditional breeding methods and/or thegeneration of mutants, or by recombinant procedures.

Some of the inventive mixtures have systemic action and can therefore beused for the protection of the plant shoot against foliar pests as wellas for the treatment of the seed and roots against soil pests. The termseed treatment comprises all suitable seed treatment techniques known inthe art, such as seed dressing, seed coating, seed dusting, seed soakingand seed pelleting.

The compounds I and the one or more compound(s) II can be appliedsimultaneously, that is jointly or separately, or in succession, thesequence, in the case of separate application, generally not having anyeffect on the result of the control measures.

The compounds I and the one or more compound(s) II can generally beapplied in a weight ratio of rom 5000:1 to 1:5000, usually in from 500:1to 1:100, preferably from 20:1 to 1:50, in particular from 5:1 to 1:20.

Depending on the desired effect, the application rates of the mixturesaccording to the invention are from 5 g/ha to 2000 g/ha, preferably from50 to 1500 g/ha, in particular from 50 to 750 g/ha.

The inventive mixtures are also suitable for the protection of the seedand the seedlings' roots and shoots, preferably the seeds, against soilpests.

Compositions, which are especially useful for seed treatment are e.g.:

A Soluble concentrates (SL, LS)

D Emulsions (EW, EO, ES)

E Suspensions (SC, OD, FS)

F Water-dispersible granules and water-soluble granules (WG, SG)

G Water-dispersible powders and water-soluble powders (WP, SP, WS)

H Gel-Formulations (GF)

I Dustable powders (DP, DS)

Conventional seed treatment formulations include for example flowableconcentrates FS, solutions LS, powders for dry treatment DS, waterdispersible powders for slurry treatment WS, water-soluble powders SSand emulsion ES and EC and gel formulation GF. These formulations can beapplied to the seed diluted or undiluted. Application to the seeds iscarried out before sowing, either directly on the seeds or after havingpregerminated the latter. Preferred are FS formulations.

In the treatment of seed, the application rates of the inventive mixtureare generally from 0.001 to 10 kg per 100 kg of seed, dependent from thedesired effect and the kind of seed. Application rates are preferablyfrom 1 to 1000 g/100 kg of seed, more preferably from 1 to 750 g/100 kg,in particular from 5 to 500 g/100 kg. The separate or joint applicationof the compounds I and II or of the mixtures of the compounds I and IIis carried out by spraying or dusting the seeds, the seedlings, theplants or the soils before or after sowing of the plants or before orafter emergence of the plants.

The invention also relates to the propagation products of plants, andespecially the seed comprising, that is, coated with and/or containing,a mixture as defined above or a composition containing the mixture oftwo or more active ingredients or a mixture of two or more compositionseach providing one of the active ingredients. The seed comprises theinventive mixtures in an amount of from 0.1 g to 10 kg per 100 kg ofseed.

The inventive mixtures are effective through both contact (via soil,glass, wall, bed net, carpet, plant parts or animal parts), andingestion (bait, or plant part) and through trophallaxis and transfer.

Preferred application methods are into water bodies, via soil, cracksand crevices, pastures, manure piles, sewers, into water, on floor,wall, or by perimeter spray application and bait.

According to another preferred embodiment of the invention, for useagainst non crop pests such as ants, termites, wasps, flies, mosquitoes,crickets, locusts, or cockroaches the inventive mixtures are preparedinto a bait preparation.

The bait can be a liquid, a solid or a semisolid preparation (e.g. agel). The bait employed in the composition is a product which issufficiently attractive to incite insects such as ants, termites, wasps,flies, mosquitoes, crickets etc. or cockroaches to eat it. Thisattractant may be chosen from feeding stimulants or para and/or sexpheromones readily known in the art.

Methods to control infectious diseases transmitted by insects (e.g.malaria, dengue and yellow fever, lymphatic filariasis, andleishmaniasis) with the inventive mixtures and their respectivecompositions also comprise treating surfaces of huts and houses, airspraying and impregnation of curtains, tents, clothing items, bed nets,tsetse-fly trap or the like. Insecticidal compositions for applicationto fibers, fabric, knitgoods, nonwovens, netting material or foils andtarpaulins preferably comprise a composition including the inventivemixtures, optionally a repellent and at least one binder.

The inventive mixtures and the compositions comprising them can be usedfor protecting wooden materials such as trees, board fences, sleepers,etc. and buildings such as houses, outhouses, factories, but alsoconstruction materials, furniture, leathers, fibers, vinyl articles,electric wires and cables etc. from ants and/or termites, and forcontrolling ants and termites from doing harm to crops or human being(e.g. when the pests invade into houses and public facilities).

In the case of soil treatment or of application to the pests dwellingplace or nest, the quantity of active ingredient ranges from 0.0001 to500 g per 100 m², preferably from 0.001 to 20 g per 100 m².

Customary application rates in the protection of materials are, forexample, from 0.01 g to 1000 g of active compound per m² treatedmaterial, desirably from 0.1 g to 50 g per m².

Insecticidal compositions for use in the impregnation of materialstypically contain from 0.001 to 95 weight %, preferably from 0.1 to 45weight %, and more preferably from 1 to 25 weight % of at least onerepellent and/or insecticide.

For use in bait compositions, the typical content of active ingredientis from 0.0001 weight % to 15 weight %, desirably from 0.001 weight % to5% weight % of active compound. The composition used may also compriseother additives such as a solvent of the active material, a flavoringagent, a preserving agent, a dye or a bitter agent. Its attractivenessmay also be enhanced by a special color, shape or texture.

For use in spray compositions, the content of the mixture of the activeingredients is from 0.001 to 80 weights %, preferably from 0.01 to 50weight % and most preferably from 0.01 to 15 weight %.

For use in treating crop plants, the rate of application of the mixtureof the active ingredients of this invention may be in the range of 0.1 gto 4000 g per hectare, desirably from 25 g to 600 g per hectare, moredesirably from 50 g to 500 g per hectare.

It was also an object of the present invention to provide mixturessuitable for treating, controlling, preventing and protectingwarm-blooded animals, including humans, and fish against infestation andinfection by pests. Problems that may be encountered with pest controlon or in animals and/or humans are similar to those described at theoutset, namely the need for reduced dosage rates, and/or enhancedspectrum of activity and/or combination of knock-down activity withprolonged control and/or resistance management.

This invention also provides a method for treating, controlling,preventing and protecting warm-blooded animals, including humans, andfish against infestation and infection by pests of the ordersSiphonaptera, Hymenoptera, Hemiptera, Orthoptera, Acarina, Phthiraptera,and Diptera, which comprises orally, topically or parenterallyadministering or applying to said animals a pesticidally effectiveamount of mixtures according to the invention.

The invention also provides a process for the preparation of acomposition for treating, controlling, preventing or protecting awarm-blooded animal or a fish against infestation or infection by pestsof the Siphonaptera, Hymenoptera, Hemiptera, Orthoptera, Acarina,Phthiraptera, and Diptera orders which comprises a pesticidallyeffective amount of a mixture according to the invention.

The above method is particularly useful for controlling and preventinginfestations and infections in warm-blooded animals such as cattle,sheep, swine, camels, deer, horses, poultry, goats, dogs and cats aswell as humans.

Infestations in warm-blooded animals and fish including, but not limitedto, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoidflies, flies, myiasitic fly larvae, chiggers, gnats, mosquitoes andfleas may be controlled, prevented or eliminated by the mixturesaccording to the invention.

For oral administration to warm-blooded animals, the mixtures accordingto the invention may be formulated as animal feeds, animal feedpremixes, animal feed concentrates, pills, solutions, pastes,suspensions, drenches, gels, tablets, boluses and capsules. In addition,the mixtures according to the invention may be administered to theanimals in their drinking water. For oral administration, the dosageform chosen should provide the animal with 0.01 mg/kg to 100 mg/kg ofanimal body weight per day of the mixture.

Alternatively, the mixtures according to the invention may beadministered to animals parenterally, for example, by intraruminal,intramuscular, intravenous or subcutaneous injection. The mixturesaccording to the invention may be dispersed or dissolved in aphysiologically acceptable carrier for subcutaneous injection.Alternatively, the mixtures according to the invention may be formulatedinto an implant for subcutaneous administration. In addition themixtures according to the invention may be transdermally administered toanimals. For parenteral administration, the dosage form chosen shouldprovide the animal with 0.01 mg/kg to 100 mg/kg of animal body weightper day of the mixture.

The mixtures according to the invention may also be applied topically tothe animals in the form of dips, dusts, powders, collars, medallions,sprays, spot-on and pour-on formulations. For topical application, dipsand sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to3000 ppm of the inventive compounds. In addition, the mixtures accordingto the invention may be formulated as ear tags for animals, particularlyquadrupeds such as cattle and sheep.

BIOLOGICAL EXAMPLES 1) Fungicidal Action

The fungicidal effect of the compound and the mixtures could bedemonstrated by the following tests:

The active compounds, separately or jointly, were prepared as a stocksolution comprising 0.25% by weight of active compound in acetone orDMSO. 1% by weight of the emulsifier Uniperol® EL (wetting agent havingemulsifying and dispersant action based on ethoxylated alkylphenols) wasadded to this solution, and the mixture was diluted with water to thedesired concentration.

The visually determined percentages of infected leaf areas wereconverted into efficacies in % of the untreated control:

The efficacy (E) is calculated as follows using Abbot's formula:E=(1−α/β)·100α corresponds to the fungicidal infection of the treated plants in % andβ corresponds to the fungicidal infection of the untreated (control)plants in %

An efficacy of 0 means that the infection level of the treated plantscorresponds to that of the untreated control plants; an efficacy of 100means that the treated plants were not infected.

The expected efficacies of mixtures of active compounds were determinedusing Colby's formula (Colby, S. R. “Calculating synergistic andantagonistic responses of herbicide Combinations”, Weeds, 15, 20-22,1967) and compared with the observed efficacies.

Colby's formula:E=x+y−x·y/100

-   E expected efficacy, expressed in % of the untreated control, when    using the mixture of the active compounds A and B at the    concentrations a and b-   x efficacy, expressed in % of the untreated control, when using the    active compound A at the concentration a-   y efficacy, expressed in % of the untreated control, when using the    active compound B at the concentration b

Use Example 1 Fungicidal Control of Brown Spot Caused by Cochliobolusmiyabeanus (Protective)

Leaves of pot-grown rice seedlings were sprayed to run-off with anaqueous suspension, containing the concentration of active ingredient asdescribed below prepared from the stock solution. The plants wereallowed to air-dry. At the following day the plants were inoculated withan aqueous spore suspension of Cochliobolus miyabeanus. Then the trialplants were immediately transferred to a humid chamber. After 6 days at22-24° C. and a relative humidity close to 100% the extent of fungalattack on the leaves was visually assessed as % diseased leaf area.

The test results show that, by virtue of strong synergism, the activityof the mixtures according to the invention is considerably higher thanhad been predicted using Colby's formula.

2) Action Against Animal Pests

The following tests demonstrate the control efficacy of compounds,mixtures or compositions of this invention on specific pests. However,the pest control protection afforded by the compounds, mixtures orcompositions is not limited to these species. In certain instances,combinations of a compound of this invention with other invertebratepest control compounds or agents are found to exhibit synergisticeffects against certain important invertebrate pests.

The analysis of synergism or antagonism between the mixtures orcompositions was determined using Colbys equation.

Use Example 2

For evaluating control of vetch aphid (Megoura viciae) through contactor systemic means the test unit consisted of 24-well-microtiter platescontaining broad bean leaf disks.

The compounds or mixtures were formulated using a solution containing75% water and 25% DMSO. Different concentrations of formulated compoundsor mixtures were sprayed onto the leaf disks at 2.5 μl, using a custombuilt micro atomizer, at two replications.

For experimental mixtures in these tests identical volumes of bothmixing partners at the desired concentrations respectively, were mixedtogether.

After application, the leaf disks were air-dried and 5-8 adult aphidsplaced on the leaf disks inside the microtiter plate wells. The aphidswere then allowed to suck on the treated leaf disks and incubated at23+1° C., 50+5% RH for 5 days. Aphid mortality and fecundity was thenvisually assessed.

In this test the compound I-2, andN-(3′,4′-dichloro-5-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide(compound 2.1), and5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine(compound 2.2) were used.

Following results were obtained

Vetch Aphid ppm Average Control % I-2 0.5 0 I-2 2.5 0 2.1 1000 0 2.2 400 I-2 + 2.1 0.5 + 1000 100*  I-2 + 2.2 2.5 + 40  75* *synergisticcontrol effect according to Colby's equation

Use Example 3

For evaluating control of boll weevil (Anthonomus grandis) the test unitconsisted of 24-well-microtiter plates containing an insect diet and20-30 A. grandis eggs.

The compounds or mixtures were formulated using a solution containing75% water and 25% DMSO. Different concentrations of formulated compoundsor mixtures were sprayed onto the insect diet at 20 μl, using a custombuilt micro atomizer, at two replications.

For experimental mixtures in these tests identical volumes of bothmixing partners at the desired concentrations respectively, were mixedtogether.

After application, microtiter plates were incubated at 23+1° C., 50+5%RH for 5 days. Egg and larval mortality was then visually assessed.

In this test the compound I-2 andN-[2-(1,1,2,3,3,3-hexafluoropropoxy)-phenyl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide(compound 3.1), andN-(3′,4′,5′-trifluorobiphenyl-2-yl)-1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide(compound 3.2) were used.

Following results were obtained

Boll Weevil ppm Average Control % I-2 0.5  0 3.1 40  0 3.2 200 50 I-2 +3.1 0.5 + 40  100* I-2 + 3.2 0.5 + 200 100* *synergistic control effectaccording to Colby's equation

Use Example 4

For evaluating control of green peach aphid (Myzus persicae) throughsystemic means the test unit consisted of 96-well-microtiter platescontaining liquid artificial diet under an artificial membrane.

The compounds or mixtures were formulated using a solution containing75% water and 25% DMSO. Different concentrations of formulated compoundsor mixtures were pipetted into the aphid diet, using a custom builtpipetter, at two replications.

For experimental mixtures in these tests identical volumes of bothmixing partners at the desired concentrations respectively, were mixedtogether.

After application, 5 to 8 adult aphids were placed on the artificialmembrane inside the microtiter plate wells. The aphids were then allowedto suck on the treated aphid diet and incubated at 23+1° C., 50+5% RHfor 3 days. Aphid mortality and fecundity was then visually assessed.For the mixture tested the results are listed in table 2.

In this test the compound I-2, and5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine(compound 2.2) andN-[2-(1,1,2,3,3,3-hexa-fluoropropoxy)-phenyl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide(compound 3.1) were used.

Following results were obtained

Green Peach Aphid ppm Average Control % I-2 0.5 0 2.2 8 0 3.1 1000 0I-2 + 2.2 0.5 + 8   75* I-2 + 3.1 0.5 + 1000 100*  *synergistic controleffect according to Colby's equation

The invention claimed is:
 1. A pesticidal mixture comprising, as activecomponents: 1) an anthranilamide compound of the formula I

in which the substituents are as defined below: B¹ is hydrogen, cyano orchlorine; B² is bromine or CF₃; and R is hydrogen or C₁-C₆-alkyl; and 2)one or more fungicidal compounds II selected from the group consistingof bixafen,5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,andN-[2-(1,1,2,3,3,3-hexafluoropropoxy)-phenyl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide,in a synergistically effective amount.
 2. The pesticidal mixture ofclaim 1, comprising the compound of formula I and the compound II in aweight ratio of from 100:1 to 1:100.
 3. The pesticidal mixture of claim1, wherein the compound of formula I is3-bromo-4′-cyano-1-(3-chloro-2-pyridyl)-2′-methyl-6′-(methylcarbamoyl)pyrazole-5-carboxanilide.4. The pesticidal mixture of claim 1, wherein the compound of formula Iis3-bromo-4′-chloro-1-(3-chloro-2-pyridyl)-2′-methyl-6′-(methylcarbamoyl)pyrazole-5-carboxanilide.5. The pesticidal mixture of claim 1, comprising two fungicidalcompounds II and the compound of formula I.
 6. A pesticidal composition,comprising a liquid or solid carrier and the mixture of claim
 1. 7. Amethod for controlling phytopathogenic harmful fungi, wherein the fungi,their habitat or the plants to be protected against fungal attack, thesoil or seed are treated with an effective amount the mixture ofclaim
 1. 8. A method for controlling insects, arachnids or nematodescomprising contacting an insect, acarid or nematode or their foodsupply, habitat, breeding grounds or their locus with the mixture ofclaim 1 in pesticidally effective amounts.
 9. A method for protectingplants from attack or infestation by insects, acarids or nematodescomprising contacting the plant, or the soil or water in which the plantis growing, with the mixture of claim 1 in pesticidally effectiveamounts.
 10. The method of claim 8, wherein the mixture is applied in anamount of from 5 g/ha to 2000 g/ha.
 11. A method for protection of seedcomprising contacting the seeds with the mixture of claim 1 inpesticidally effective amounts.
 12. The method of claim 11 wherein themixture is applied in an amount of from 0.001 g to 10 kg per 100 kg ofseeds.
 13. Seed, comprising the mixture of claim 1 in an amount of from0.1 g to 10 kg per 100 kg of seeds.
 14. A method for controllingphytopathogenic harmful fungi, wherein the fungi, their habitat or theplants to be protected against fungal attack, the soil or seed aretreated with an effective amount of 1) an anthranilamide compound of theformula I

in which the substituents are as defined below: B¹ is hydrogen, cyano orchlorine; B² is bromine or CF₃; and R is hydrogen or C₁-C₆-alkyl; and 2)one or more fungicidal compounds II selected from the group consistingof bixafen,5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,andN-[2-(1,1,2,3,3,3-hexafluoropropoxy)-phenyl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide,and wherein the compound of formula I and the compound II are appliedsimultaneously, separately, or in succession.